Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
  • C08G65/2645—Metals or compounds thereof, e.g. salts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
  • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
  • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
  • C08G18/6258—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids the acid groups being esterified with polyhydroxy compounds or epoxy compounds during or after polymerization
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
  • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
  • C08G65/08—Saturated oxiranes
  • C08G65/10—Saturated oxiranes characterised by the catalysts used
  • C08G65/105—Onium compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
  • C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
  • C08G65/2669—Non-metals or compounds thereof

Definitions

• the present invention relates to a new process for the preparation of hydroxyl-containing alkoxylation products of organic carboxylic acids using special phase transfer catalysts as accelerators for the alkoxylation reaction and the use of the alkoxylation products as reactants for organic polyisocyanates in the production of polyurethane plastics.
• Any organic compounds which have at least one free carboxyl group are suitable for the process according to the invention. This means that both low molecular weight organic carboxylic acids and oligomeric or polymeric carboxyl group-containing compounds can be used in the process according to the invention.
• Suitable low molecular weight compounds containing carboxyl groups are, for example, aliphatic carboxylic acids with 1 to 36, preferably 1 to 18, preferably 1 to 18 carbon atoms, such as formic acid, acetic acid, propionic acid, the isomeric butyric acids, ethylhexanoic acid, stearic acid, lactic acid, ricinoleic acid, which optionally have olefinically unsaturated and optionally alcoholic hydroxyl groups.
• oleic acid dimerized oleic acid, maleic acid, fumaric acid, adipic acid, succinic acid or citric acid
• cycloaliphatic carboxylic acids having 6 to 8 carbon atoms such as cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid or p-hydroxy-cyclohexanecarboxylic acid, optionally containing olefinically unsaturated and / or optionally alcoholic hydroxyl groups as substituents
• aromatic carboxylic acids with 6 to 8 carbon atoms such as phthalic acid, isophthalic acid, terephthalic acid or benzoic acid.
• Suitable oligomeric or polymeric carboxylic acids include, for example, carboxyl-containing polyesters or alkyd resins such as those obtained in the polycondensation of polyhydric alcohols, optionally in a mixture with monohydric alcohols with polybasic carboxylic acids, optionally in a mixture with monobasic carboxylic acids or their esters , and as defined for example in Römpp's Chemielexikon, Volume 1, page 202, Franckh'sche Verlag Buchmaschine, Stuttgart (1966), or by DH Solomon, The Chemistry of Organic Filmformers, pages 75-101, John Wiley & Sons Inc. New York, (1967).
• the carboxyl group-containing polyesters or alkyd resins which can be used in the process according to the invention generally have acid numbers of 10 to 300 mg KOH / g substance and a number average molecular weight of 1000 to 20,000 (determined up to molecular weights of 5000 by vapor pressure osmometry; at Molecular weights over 5000 determined by membrane osmometry).
• Alcohols suitable for producing the "acidic" polyesters or alkyd resins are, for example, aliphatic, cycloaliphatic and / or aromatic alcohols having 1 to 6, preferably 1 to 4, OH groups bonded to non-aromatic C atoms and 1 to 24 C atoms per molecule, e.g. Glycols such as ethylene glycol, propylene glycol,
• Acid components suitable for the synthesis of the alkyd resins or polyesters are aliphatic, cycloaliphatic saturated or unsaturated and / or aromatic polybasic carboxylic acids, preferably di-, tri- and tetracarboxylic acids with 4-12 carbon atoms per molecule or their esterifiable derivatives (e.g. anhydrides or Esters), e.g.
• Phthalic anhydride isophthalic acid, terephthalic acid, tetrahydro- and hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, adipic and succinic anhydride, and also halogenated acids such as chlorophthalic and heteroacid.
• Monocarboxylic acids or monocarboxylic esters suitable for the production of the polyesters or alkyd resins are aliphatic, cycloaliphatic saturated and unsaturated and / or aromatic monocarboxylic acids with 6-24 carbon atoms per molecule, such as benzoic acid, butylbenzoic acid, tolylic acid, hexahydrobenzoic acid, abietic acid, lactic acid and fatty acids the same as linseed oil, soybean oil, wood oil, safflower oil, castor oil, castor oil, cottonseed oil, peanut oil, tall oil fatty acid, linseed oil fatty acid, soybean oil, wood oil, safflower oil and ricin oil fatty acid and from natural, unsaturated oils or fatty acids Products conjugated or isomerized; suitable saturated fatty acids are, for example, coconut fatty acids and 2-ethylhexanoic acid.
• polyesters and alkyd resins are prepared in a manner known per se by condensation using the customary processes.
• the raw material mixtures are allowed to react at from 140 to 250 ° C. in a protective gas atmosphere, for example N 2 ', with elimination of water until the desired acid number is reached.
• a protective gas atmosphere for example N 2 '
• particularly preferred compounds containing oligomeric or polymeric carboxyl groups for the process according to the invention are copolymers of acrylic acid, methacrylic acid, maleic acid or their derivatives or of mixtures of these acids with other unsaturated monomers of the type mentioned below with acid numbers from 20 to 500 and hydroxyl numbers from 0 up to 130 mg KOH / g substance.
• Derivatives of maleic acid include monoamides or monoesters, which e.g. can be prepared by reacting maleic anhydride with amines such as ethylamine or n-butylamine or alcohols such as ethanol or n-butanol.
• copolymers those which contain 3 to 50% by weight of acrylic acid and / or methacrylic acid and 10 to 90% by weight of styrene, methyl methacrylate, acrylonitrile and / or methacrylonitrile are particularly preferred,
• acrylate resins can be prepared by polymerization using customary methods, preferably in solution or in bulk.
• Suitable solvents are aromatics such as benzene, toluene, xylene, chlorobenzene, esters such as ethyl acetate, butyl acetate, methylglycol acetate, ethylglycol acetate, methoxypropylacetate, ethers such as butylglycol, tetrahydrofuran, dioxane, ethylglycol ether, ketones such as acetone, methylethylketone, or halogenated trichloromethane or halogenated trichloromethane or halogenated solvents such as methane chloromethane or halogenated methane chloride . If the apolar solvents mentioned by way of example have insufficient solubility, they are advantageously used in a mixture with the polar solvents mentioned by way of example.
• the polyacrylate resins can be prepared either continuously or batchwise. If you look into a polymerization reactor evenly and continuously metering in the monomer mixture and the initiator and at the same time continuously discharging the corresponding amount of polymer, a steady state is established in the reactor after a relatively short start-up period.
• Suitable initiators for the preparation of the polyacrylate resins are those compounds whose half-lives of radical decomposition at 80 to 180 ° C. are between 0.01 and 400 minutes.
• the copolymerization reaction takes place in the last-mentioned temperature range, preferably between 100 ° C. and 160 ° C., under a pressure of 10 3 to 2,104 mbar, the exact temperature depending on the type of initiator.
• the initiators are used in amounts of 0.05 to 6% by weight, based on the total amount of monomers. In general, at least 98% of the monomers used are converted.
• Suitable initiators are, for example, aliphatic azo compounds such as azoisobutyronitrile and peroxides such as dibenzoyl peroxide, tert-butyl perpivalate, tert-butyl per- 2-ethylhexanoate, tert-butyl perbenzoate, tert-butyl hydroperoxide, di-tert-butyl peroxide, cumene hydroperoxide and dicyclohexyl and dibenzyl peroxydicarbonate.
• aliphatic azo compounds such as azoisobutyronitrile and peroxides such as dibenzoyl peroxide, tert-butyl perpivalate, tert-butyl per- 2-ethylhexanoate, tert-butyl perbenzoate, tert-butyl hydroperoxide, di-tert-butyl peroxide, cumene hydroperoxide and dicyclohe
• regulators can be used to regulate the molecular weight of the acrylic resin, e.g. n-dodecyl mercaptan, diisopropylxanthogen disulfide, di (methylene trimethylolpropane) xanthogen disulfide and thioglycol.
• Thioglycol is particularly preferred because of its hydroxyl group.
• the regulators are added in amounts of 0.1 to 3% by weight, based on the monomer mixture.
• the monomers are incorporated into the copolymer in essentially the same proportions as used for the polymerization, the copolymerized units being essentially randomly distributed.
• the carboxyl group-containing acrylate polymers have average molecular weights M GPC of approximately 1000 to 40,000, preferably 3000 to 20,000, and their 40-80% by weight solutions in ethyl glycol acetate have a viscosity of approximately 10 to 100,000 mPa at 20 ° C. .s, depending on the added amount and concentration of regulator. Furthermore, the carboxyl group-containing acrylate polymers have molecular nonuniformities U of 0.5-3, preferably 0.5-2.
• Alkylene oxides suitable for the process according to the invention are any organic compounds which form the structural unit exhibit. Any compounds of the formula are therefore suitable for which R and R 'represent identical or different radicals and are hydrogen, an alkyl group with 1 to 16 carbon atoms, a cycloalkyl group with 5 to 12 carbon atoms or an aryl group with 6 to 12 carbon atoms, the substituents mentioned also being heteroatoms or functional substituents , in particular may have hydroxyl substituents.
• ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide, glycidyl alcohol or versatic acid glycidyl ester are particularly well suited.
• Ethylene oxide and propylene oxide or mixtures of these alkylene oxides are particularly preferably used.
• alkyl radicals include not only the purely aliphatic alkyl radicals but also substituted alkyl radicals such as aralkyl radicals or To understand cycloalkyl radicals, the information given regarding the number of carbon atoms relating to the radicals as a whole. However, preference is given to those quaternary salts of the type mentioned which have at most one aralkyl radical or cycloalkyl radical in addition to three purely aliphatic alkyl radicals. The corresponding purely aliphatic quaternary ammonium salts are particularly preferred.
• quaternary ammonium salts examples include tetraethyl ammonium iodide, tetrabutylammonium bromide, tetrabutylphosphonium bromide, methyltrioctylammonium chloride, benzyldimethyltetradecylammonium chloride, benzyltributylammonium chloride, benzyltriethylammonium chloride, Cyclohexyltriethylammoniumchlorid, trimethylstearylammonium chloride, tetradecylammonium bromide or Tetrastearylammoniumchlorid.
• Particularly suitable catalysts are 1: 1 complexes of (i) basic sodium or potassium compounds and (ii) 1,4,7,10,13-pentaoxacyclopentadecane ("15-crown-5") or 1,4,7 , 10,13,16-Hexaoxacyclooctadecan ("18-Krone-6").
• “1: 1 complexes” include complexes of equimolar amounts of a basic sodium or potassium compound 15-crown-5 or 18-crown-6 to understand. The complexation of the sodium compounds takes place with the former, the complexation of the potassium compounds with the latter cyclic polyether.
• Suitable basic sodium or potassium compounds are any compounds of the alkali metals mentioned, the aqueous solution of which has a pH of at least 7.5 in a molar concentration and the anion of which opens the oxirane ring in the desired manner.
• Suitable basic compounds are, for example, sodium or potassium carboxylates with preferably 1 to 12 C atoms, alcoholates with preferably 1 to 8 C atoms, phenolates with preferably 6 to 10 C atoms, carbonates and hydroxides. These are e.g. the formates, acetates, propionates, 2-ethylhexanoates, n-dodecanoates, caprylates, methylates, ethylates, butylates, hexylates, phenolates, tert-butylphenolates, carbonates and hydroxides of the metals mentioned.
• the preferred basic compounds include potassium hydroxide and potassium acetate.
• the cyclic polyethers used for complex formation are known compounds. Their preparation can, for example, according to G. Johns, CJ Ransom, CB Reese, Synthesis (1976), page 515.
• Components (i) and (ii) are preferably used in equimolar amounts in the preparation of the 1: 1 complexes. Of course, it would also be possible to work in other proportions, but this would have the consequence that either the basic alkali metal compound or the cyclic polyether is present in excess. How easy it is to see Such a procedure would be of little use, since the respective excess would have no or only a comparatively poor catalytic effect.
• components (i) and (ii) are generally used in amounts such that 0.4 to 40, preferably 0.8 to 20% by weight solutions of the complexes are present . It is precisely one of the main advantages of the catalysts that they are soluble in such comparatively high concentrations in the solvents exemplified above.
• the catalyst component (iii) is acyclic organic compounds which meet the above-mentioned criteria, in particular those which
• alkylene oxide units of the type mentioned preferably ethylene oxide and optionally propylene oxide units in the form of one or more polyether chains each having at least 3, preferably at least 5, alkylene oxide units,
• alkylene oxide units of the type mentioned incorporated within polyether chains at least 50%, preferably at least 80% of all alkylene oxide units present being ethylene oxide units and having a molecular weight of 238 to 3000, particularly preferably of 282 to 1000.
• Technical mixtures of polyethylene glycols with an average molecular weight of 350 to 450 are particularly preferred.
• suitable catalyst components (iii) are 1- to 3-valent polyether alcohols corresponding to these definitions, such as those obtained in a manner known per se by alkoxylation, in particular ethoxylation, of suitable starter molecules such as monohydric alcohols such as methanol, ethanol, n- or i-propanol , n-, i-, sec- or tert-butanol, of water or of at least divalent starter molecules such as ethylene glycol, propane diol (1,2), propanediol (1,3), butane, pentane or hexanediols, glycerol, trimethylolethane or trimethylolpropane can be obtained.
• suitable polyethers of the type mentioned by way of example whose terminal hydroxyl group (s) have been encoded, for example, by alkylation, acylation and / or urethanization, so that there are no longer any hydroxyl end groups.
• the terminal hydroxyl group (s) of the above-mentioned polyether alcohols are encoded by alkylation, for example by reacting the polyether alcohols with alkylating agents such as, for example, dimethyl sulfate, C 1 -C 4 -alkyl halides or benzyl halide; encryption by an acylation reaction by reaction with acylating agents such as acetic anhydride, acetyl chloride or benzoyl chloride; encryption by urethanization by reaction with monovalent isocyanates such as methyl, ethyl, hexyl or phenyl isocyanate.
• alkylating agents such as, for example, dimethyl sulfate, C 1 -C 4 -alkyl halides or benzyl halide
• acylating agents such as acetic anhydride, acetyl chloride or benzoyl chloride
• encryption by urethanization by reaction with monovalent isocyanates such as
• aldehydes such as formaldehyde, acetaldehyde or benzaldehyde in the sense of acetalization
• optionally substituted methylene oxide units are introduced into the polyethers.
• the compounds (iii) corresponding to the above definitions also meet these definitions, for example because the alkylene oxide units are too low , do not contain appropriate compounds, the amount of such mixtures must of course be measured so that the above proportions of components (i) and (iii) are observed.
• the reaction between components (i) and (iii), ie the complex formation generally takes place spontaneously at a temperature of about 10 to 60 ° C., in particular if components (i) and (iii) which are compatible with one another are used in the absence of solvents .
• the complexes can also be formed in the presence of solvents or solvent mixtures of the type exemplified above.
• the complexed potassium compounds described under b) and c) represent the particularly preferred accelerators to be used in the process according to the invention.
• the accelerators are either used as a solution in a suitable orga African solvents such as aromatics, esters, ethers, ketones, halogen-containing solvents of the above-mentioned type or in bulk or, in the case of the complex compounds mentioned under b) and c), also in the form of their individual components, which in turn, if appropriate, in a solvent of the examples mentioned Can be used in kind, the complex formation taking place in situ.
• the amount of the accelerators is generally 0.01 to 2.0% by weight, preferably 0.02 to 1.0% by weight, based on the amount of the organic compound having carboxyl groups.
• the process according to the invention is preferably carried out in the presence of a solvent or solvent mixture.
• Suitable solvents are, for example, those mentioned above in connection with the production of the acrylate resins.
• the alkoxylation reaction according to the invention is generally carried out within the temperature range from 40 to 200 ° C., preferably between 100 ° C. and 200 ° C., if appropriate under pressure.
• the procedure is such that a, for example 40 to 80% by weight solution of the carboxyl group-containing organic compound, which already contains the accelerator essential to the invention, for a period of 0.2 to 10 hours, preferably 1 to 5 hours, the alkylene oxide or the alkylene oxide mixture is metered in continuously or batchwise and then the reaction mixture is added for a further 2 to 15 hours, preferably stirred for 4 to 10 hours.
• the amount of the alkylene oxide is preferably such that the equivalent ratio of alkylene oxide to carboxyl groups is 0.5: 1 to 2.0: 1, preferably 0.9: 1 to 1.1: 1.
• the aim is on the one hand to achieve the most selective esterification of the carboxyl groups with the formation of hydroxyalkyl ester groups, and on the other hand the formation of reaction products which usually have undesired ether groups (by alkoxylation of hydroxyl groups) and the possible formation of ester groups to largely rule out an esterification reaction between the hydroxyl and carboxyl groups present in the reaction mixture.
• this is achieved on the one hand by the low concentration of the accelerators essential to the invention and on the other hand by the gradual addition of the alkylene oxide in order to avoid an excessively high local epoxy concentration.
• the process according to the invention indeed allows a largely selective conversion of the carboxyl groups into hydroxyalkyl ester groups, so that, with the particularly preferred use of the alkylene oxides, reaction products with high hydroxyl number and low acid number, based on the acid groups, result in equivalent amounts.
• the process products according to the invention based on the carboxyls exemplified above Group-containing polyesters or alkyd resins are valuable reaction partners for organic polyisocyanates in the production of polyurethane plastics, in particular, because of their high content of hydroxyl groups and their low content of carboxyl groups Since the alkoxylation reaction according to the invention does not significantly increase the molecular weight of the oligomeric or polymeric starting compounds, the molecular weights of the process products according to the invention based on the oligomeric or polymeric starting materials are within the ranges mentioned above with regard to the starting materials.
• the hydroxyl numbers of the process products according to the invention based on the oligomeric or polymeric starting compounds mentioned are generally within the range from 20 to 250, preferably 30 to 220 (mg KOH / g substance) and the acid numbers between 2 and 25 (mg KOH / g substance), however, it can be said that due to the modification according to the invention, the acid number is generally less than half the acid number of the corresponding starting material.
• the alkoxylating agents which are particularly preferred according to the invention, are used in equivalent amounts, based on the carboxyl groups present in the starting materials, the acid number is generally reduced to less than 10% of the starting value by the process according to the invention.
• the process products according to the invention based on the oligomeric or polymeric starting compounds mentioned above as examples, particularly preferably the process products according to the invention based on the copolymers of acrylic acid and / or methacrylic acid mentioned above as examples, are valuable starting materials for the production of polyurethane plastics.
• the invention therefore also relates to the use of the alkoxylation products containing hydroxyl groups obtained by the process according to the invention as reactants for organic polyisocyanates in a form which may be blocked with blocking agents for isocyanate groups in the production of polyurethane plastics.
• Polyisocyanates suitable for the use according to the invention are, in particular, the so-called lacquer polyisocyanates of the prior art, the production of which is described, for example, in US Pat. No. 3,124,605, US Pat. No. 3,358,010, US Pat. No. 3,903,126, US Pat. No. 3,903,127, US Pat. PS 3 976 622, US Pat. No. 3 183 112, US Pat. No. 3 394 111, US Pat. No. 3 645 979 or US Pat. No. 3 919 218 or in GB PS 1 060 430, GB PS 1 234 972, GB -PS 1 506 373 or GB-PS 1 458 564.
• lacquer polyisocyanates are preferably polyisocyanates containing biuret groups, urethane groups or isocyanurate groups based on simple, commercially available diisocyanates such as hexamethylene diisocyanate, 2,4- and / or 2,6-diisocyanatotoluene, 2,4'- and / or 4,4'-diisocyanatodicyclohexylmethane or isophorone diisocyanate.
• the polyisocyanates containing biuret groups are generally reaction products of hexamethylene diisocyanate with water or with water-releasing compounds. These are in particular mixtures of tris (isocyanatohexyl) biuret with its higher homologues. These biuret polyisocyanates are the lacquer polyisocyanates to be used with particular preference.
• the polyisocyanates containing urethane groups are, in particular, reaction products of 2,4- and / or 2,6-diisocyanatotoluene or of isophorone diisocyanate with inadequate amounts of polyhydric alcohols, in particular trimethylolpropane, optionally in a mixture with propanediols or butanediols.
• lacquer polyisocyanates containing isocyanurate groups are preferably trimerizates or mixed trimerizates of the simple diisocyanates exemplified above which have isocyanate groups.
• isocyanate component with blocking agents for isocyanate groups, e.g. Phenols, oximes such as cyclohexanone oxime, ⁇ -caprolactam, diethyl malonate or ethyl acetoacetate are used in a blocked form, so that heat-crosslinkable stoving lacquers result.
• blocking agents for isocyanate groups e.g. Phenols, oximes such as cyclohexanone oxime, ⁇ -caprolactam, diethyl malonate or ethyl acetoacetate are used in a blocked form, so that heat-crosslinkable stoving lacquers result.
• the process products according to the invention in particular when using the process products according to the invention based on the oligomeric or polymeric starting materials mentioned above as examples in the production of two-component polyurethane lacquers, the process products according to the invention and the lacquer polyisocyanates mentioned as examples are used in amounts such that each hydroxyl group of the process products according to the invention 0.5 to 2, preferably 0.7 to 1.3, optionally blocked isocyanate groups are eliminated.
• reaction partners for organic polyisocyanates known from polyurethane coating chemistry can of course also be used in the use according to the invention.
• auxiliaries and additives customary in polyurethane coating technology such as e.g. Solvents, leveling agents, viscosity-controlling additives, matting agents, accelerators, pigments or fillers can also be used.
• any method of lacquer technology such as spraying, brushing, dipping, printing or rolling, can be used, substrates of any kind such as metals, wood, masonry, concrete, glass, ceramics, Plastics, textiles or paper can be layered.
• the ready-to-use two-component polyurethane lacquers are characterized by long service lives and fast drying times, as well as good flow and color fidelity or light fastness and excellent mechanical properties of the coatings obtained with them, even when using lacquer polyisocyanates with free isocyanate groups.
• the lacquer coatings are cured at 20 to 140 ° C, preferably at 20 to 60 ° C, while when using blocked polyisocyanates, stoving lacquers result which are cured at 120 to 180 ° C.
• Example 3 The procedure is as described in Example 3, with the difference that no catalyst is used.
• the dropping time of the propylene oxide at 100 to 110 ° C is 12 hours.
• the stirring time is 5 hours at 100 to 110 ° C. After cooling you get one light brown solution with an acid number of 37.5 and a hydroxyl number (DIN 53 240) of 154 (OHZ calc. 170).
• 6250 g of ethyl glycol acetate are placed in a 40 liter stirred autoclave under a nitrogen atmosphere and heated to 140 ° C. At this temperature, which is kept under control, a monomer mixture of 3720 g of acrylic acid, 6000 g of styrene, 3000 g of methyl methacrylate and 1940 g of 2-ethylhexyl acrylate and an initiator mixture of 600 g of di-t-butyl peroxide and 4000 g of ethyl glycol acetate are added within 4 hours Exclusion of air added. The mixture is then reactivated with a mixture of 30 g of di-t-butyl peroxide and 100 g of ethyl glycol acetate and polymerized out within about 4 hours.
• the isocyanate content of the solution is 16.5%.
• the individual components are used in amounts such that an NCO / OH equivalent ratio of 1: 1 results.
• lacquers described in the examples below were clear lacquers with a solids content of approximately 40% by weight.
• the additional dilution was carried out by using a mixture of ethylglycol acetate, xylene, (R) Solvesso 100 and n-butyl acetate (weight ratio 4 : 4: 1: 1).

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Polyurethanes Or Polyureas (AREA)
• Polyethers (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 1984
  • 1984-04-26 DE DE19843415531 patent/DE3415531A1/de not_active Withdrawn
• 1985
  • 1985-04-11 US US06/722,567 patent/US4645817A/en not_active Expired - Fee Related
  • 1985-04-11 CA CA000478897A patent/CA1233480A/fr not_active Expired
  • 1985-04-15 DE DE8585104528T patent/DE3571444D1/de not_active Expired
  • 1985-04-15 EP EP85104528A patent/EP0159643B1/fr not_active Expired
  • 1985-04-15 AT AT85104528T patent/ATE44537T1/de not_active IP Right Cessation
  • 1985-04-25 JP JP60087681A patent/JPS60237029A/ja active Pending
  • 1985-04-25 ES ES542572A patent/ES8607350A1/es not_active Expired

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